Samarium cobalt and neodymium iron boride magnets and methods of manufacturing same

ABSTRACT

In one embodiment, a magnet includes a three-dimensional structure with nanoscale features, where the three-dimensional structure has a near net shape corresponding to a predefined shape.

The United States Government has rights in this invention pursuant toContract No. DE-AC52-07NA27344 between the United States Department ofEnergy and Lawrence Livermore National Security, LLC for the operationof Lawrence Livermore National Laboratory.

FIELD OF THE INVENTION

The present invention relates to samarium cobalt and neodymium ironboride magnets, and more particularly, this invention relates to methodsof manufacturing samarium cobalt and neodymium iron boride magnets.

BACKGROUND

Permanent magnets are central to modern technology by being essentialfor energy efficient, lightweight devices such as cell phones, ear buds,and laptops, and being essential in large quantities (e.g. kilogram toton quantities) for high efficiency and renewable energy applicationssuch as wind turbines, electric drive, and hybrid motors. The use ofpermanent magnets in electric motors allows higher efficiency in asignificantly smaller mass and volume. Moreover, high energy productsthat are maintained at high temperatures, e.g. electric motors, utilizea class of permanent magnets that include Samarium Cobalt (SmCo₅)magnets. In the United States, electric motors consume approximately 15%of total electricity usage. Thus, even small increases in electricalmotor efficiency have a sizable impact on reduced energy costs andreduced CO₂ emissions. For example, a 1% efficiency improvementtranslates into savings of hundreds of millions of dollars and areduction of 2.2 million metric tons of CO₂ emissions.

Permanent magnets may be graded for merit according to a measure of(BH)_(max) energy product which represents maximum useable energy storedin the magnet. The energy product is a combination of the remanentmagnetization (M_(r)), a measure of the average magnetism (totalmagnetic moment divided by the volume of the magnet), and the coercivity(H_(e)), a measure of the resistance to becoming demagnetized. Highcoercivity at ambient room temperature is important for motorapplications because coercivity tends to decline with temperature inconventional magnets. A magnet with high coercivity would enable optimalcoercivity at elevated temperatures. Progress in magnetic materials overthe past century has been ascribed to a mastery of high coercivity andthe related magnetocrystalline anisotropy. Conventional magnets withhigh coercivity are typically composed of rare earth element-transitionmetal (RE-TM) materials, where the orbital electron structure containsunpaired electrons in the 4f subshell (4f electrons) that may contributeto high magnetocrystalline anisotropy of the RE-TM, and containselectrons in the 3d subshell (3d electrons) that may contribute to highmagnetization and Curie temperature of the RE-TM. Typically the realizedcoercivity of conventional magnets reaches only 25-30% of the maximumachievable coercivity, after a long optimization of the magneticmicrostructure. Moreover, ideally, magnetic material would possess ahigh coercivity at working temperatures for motor applications which runat temperatures greater than 150° C.

Currently the only two high energy product magnetic materials aresuitable for motor applications and are based on RE-TM materials:Neodymium Iron Boride (Nd₂Fe₁₄B or Nd—Fe—B) often doped with Dy or Tb,and Samarium cobalt (SmCo₅ or Sm₂Co₁₇) frequently alloyed with smallamounts of Fe, vanadium (V), nickel (Ni), and copper (Cu). Nd—Fe—Bmagnets, the most widely used permanent magnet material, are used inlarge quantities in hybrid and electric drive motors. However, manycritical materials in these permanent magnets are expensive andsusceptible to supply disruption. For example, critical rare earthelements Sm, Nd, and Dy, which provide increased energy efficiencies ofNd—Fe—B and SmCo₅ magnets, are mined primarily in China. Therefore, forreasons of national and economic security as well as general efficiencyof manufacture, it is desirable to improve manufacturing of thepermanent magnets to reduce waste and consumption of the criticalmaterials.

Moreover, methods remain elusive to manufacture permanent magnets withthe light REs being naturally available in abundant supply, e.g. SmCo.Conventional permanent magnets tend to rely on heavy REs, e.g. Tb andDy, to increase the coercivity of Nd—Fe—B magnets for functioning incurrent motor applications. Magnets based on SmCo have higherenvironmental stability than Nd—Fe—B magnets. The much higher T_(c) ofSmCo may provide a desirable option for high temperature applications,such as motors and generators.

Moreover, it would also be desirable to minimize waste and cost of REsduring the manufacture of magnets as mining for some REs can beenvironmentally sensitive. Of SmCo formulations, SmCo₅, with a hexagonalcrystal structure (similar to the crystal structure of CaCO, has thehighest known magnetocrystalline anisotropy (and thus very hightheoretical coercivity) and a high T_(c) of 1020 K. It would bedesirable to improve the material formulation of SmCo₅ permanent magnetsas well as the process of manufacturing SmCo₅ magnets in order to reducecosts and waste.

Conventional manufacturing of permanent magnets includes a powderedmetallurgical process followed by subtractive machining to a desiredsize. Traditional bulk SmCo₅ and Nd—Fe—B based alloys are typically madeinto permanent magnets following the metallurgical process of sinteringpressed powders into large blocks. After heat treatment, these blocksare machined into smaller parts with dicing, grinding, and othermechanical techniques. RE magnets are very brittle and readily chip andfracture, so precision machining of magnets to high tolerancessignificantly adds to production costs. The debris and waste (e.g.swarf, kerf, etc.) resulting from machining small magnets to theirdesired size and shape often exceeds 60% of the starting materialvolume. Thus, machining permanent magnets using a subtractive processresults in significant waste of the valuable material.

Designing dies of a specific desired shape for custom magnets, however,is expensive. Designing and producing individual dies can cost up tothousands to tens of thousands of dollars. Moreover, new products oftenuse many different magnet shapes for prototyping, and only using about ahundred prototypes of each shape, so using custom dies for relativelysmall numbers of magnets can be cost prohibitive.

Alternatively, conventional manufacturing of permanent magnets includesa process of blending magnet material with polymers to make bondedmagnets for near net-shape manufacturing of more complex magnet shapes.Bonded magnets have been developed to attempt to overcome thedifficulties, wastes, and costs associated with traditional machining ofpermanent magnets. Bonded magnets are magnet particles combined with apolymer binder that can be extruded, molded, or rolled into sheets andgeometric shapes. However, introducing a polymer binder reduces theenergy product of the magnet thereby resulting in a larger volume magnetto achieve the same properties as machined magnets. Moreover, thetemperature tolerance of bonded magnets may also be reduced compared tomachined magnets.

Thus, methods for manufacturing permanent magnets with reduced waste (astypically generated by subtractive machining) and reduced loss of energy(as typically occurs with blending with polymers) have been elusive.

SUMMARY

In one embodiment, a magnet includes a three-dimensional structure withnanoscale features, where the three-dimensional structure has a near netshape corresponding to a predefined shape.

In another embodiment, a method of making a permanent magnet includesforming a three dimensional structure comprising oxidized precursormetal particles, heating the formed three dimensional structure in anatmosphere comprising a calcium vapor and a gas for reducing theoxidized precursor metal particles of the three dimensional structure,and applying a magnetic field to the reduced precursor metal particlesof the three dimensional structure.

In yet another embodiment, a method of making a thin foil magnetincludes forming a thin foil having a plurality of layers of oxidizedprecursor metal nanoparticles, reducing the oxidized precursor metalnanoparticles of the thin foil in an atmosphere comprising a calciumvapor and a gas, and applying a magnetic field to the reduced precursormetal nanoparticles of the thin foil. The forming of the thin foilhaving a plurality of layers of oxidized precursor metal nanoparticlesincludes forming a first layer of oxidized precursor metal nanoparticleson a substrate, where the oxidized precursor metal nanoparticles aresuspended in a solution, evaporating a liquid component of the solutionfrom the first layer of oxidized precursor metal nanoparticles, afterthe evaporating, forming at least one second layer of oxidized precursormetal nanoparticles above the first layer of oxidized precursor metalnanoparticles, evaporating the liquid component of the solution from theat least one second layer of oxidized precursor metal nanoparticleswherein the thin foil has a plurality of layers of oxidized precursormetal nanoparticles, where the thin foil has a pre-defined thickness.

Other aspects and advantages of the present invention will becomeapparent from the following detailed description, which, when taken inconjunction with the drawings, illustrate by way of example theprinciples of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic drawing of a thin foil magnet, according to oneembodiment.

FIG. 2 is a flow chart of a method, according to one embodiment.

FIG. 3A is a schematic drawing of a reducing operation of a method,according to one embodiment.

FIG. 3B is an image of a reducing apparatus, according to oneembodiment.

FIG. 3C is a schematic drawing of an annealing operation, according toone embodiment.

FIG. 4A is a flow chart of a method, according to one embodiment.

FIG. 4B is a flow chart of step 402 of FIG. 4A.

FIG. 5A is a plot of the maximum energy product and magnetic coercivityof magnets formed at various temperatures, according to one embodiment.

FIG. 5B is a plot of moment compared to magnetic field of magnets formedat various temperatures, according to one embodiment.

DETAILED DESCRIPTION

The following description is made for the purpose of illustrating thegeneral principles of the present invention and is not meant to limitthe inventive concepts claimed herein. Further, particular featuresdescribed herein can be used in combination with other describedfeatures in each of the various possible combinations and permutations.

Unless otherwise specifically defined herein, all terms are to be giventheir broadest possible interpretation including meanings implied fromthe specification as well as meanings understood by those skilled in theart and/or as defined in dictionaries, treatises, etc.

It must also be noted that, as used in the specification and theappended claims, the singular forms “a,” “an” and “the” include pluralreferents unless otherwise specified.

A nanoscale is defined as having a diameter or length less than 1000nanometers (nm).

The following description discloses samarium cobalt and neodymium ironboride magnets and/or related systems and methods.

In one general embodiment, a magnet includes a three-dimensionalstructure with nanoscale features, where the three-dimensional structurehas a near net shape corresponding to a predefined shape.

In another general embodiment, a method of making a permanent magnetincludes forming a three dimensional structure comprising oxidizedprecursor metal particles, heating the formed three dimensionalstructure in an atmosphere comprising a calcium vapor and a gas forreducing the oxidized precursor metal particles of the three dimensionalstructure, and applying a magnetic field to the reduced precursor metalparticles of the three dimensional structure.

In yet another general embodiment, a method of making a thin foil magnetincludes forming a thin foil having a plurality of layers of oxidizedprecursor metal nanoparticles, reducing the oxidized precursor metalnanoparticles of the thin foil in an atmosphere comprising a calciumvapor and a gas, and applying a magnetic field to the reduced precursormetal nanoparticles of the thin foil. The forming of the thin foilhaving a plurality of layers of oxidized precursor metal nanoparticlesincludes forming a first layer of oxidized precursor metal nanoparticleson a substrate, where the oxidized precursor metal nanoparticles aresuspended in a solution, evaporating a liquid component of the solutionfrom the first layer of oxidized precursor metal nanoparticles, afterthe evaporating, forming at least one second layer of oxidized precursormetal nanoparticles above the first layer of oxidized precursor metalnanoparticles, evaporating the liquid component of the solution from theat least one second layer of oxidized precursor metal nanoparticleswherein the thin foil has a plurality of layers of oxidized precursormetal nanoparticles, where the thin foil has a pre-defined thickness.

A list of acronyms used in the description is provided below.

-   -   3D Three dimensional    -   Ar Argon    -   B Boron    -   (BH)_(max) Maximum energy stored in a magnet    -   C Celsius    -   cm centimeter    -   cm² centimeter squared    -   Co Cobalt    -   CO₂ Carbon dioxide    -   Cu Copper    -   Dy Dysprosium    -   EPD Electrophoretic deposition    -   FSP Flame spray pyrolysis    -   g gram    -   g/cm³ gram/centimeter cubed, density    -   H_(c) coercivity    -   H₂ hydrogen gas    -   H_(c) Coercivity    -   K Kelvin    -   kOe Kilo oerested    -   KCl Potassium chloride    -   DIW Direct ink write    -   M_(r) Remnant magnetization    -   mg milligram    -   MGOe Mega-Gauss-Oersted    -   ml milliliter    -   mm millimeter    -   Nd—Fe—B Neodymium Iron Boride    -   Ni Nickel    -   nm nanometer    -   Oe oerested    -   RE-TM rare earth element-transition metal    -   rpm revolutions per minute    -   Sm Samarium    -   SmCo₅ Samarium Cobalt    -   s⁻¹ per second    -   Tb Terbium    -   T_(c) Critical temperature    -   μm micron    -   V Vanadium    -   v volts    -   vol volume

Conventional approaches to manufacturing permanent magnets involvesubtractive manufacturing methods which result in significant waste ofmaterials and incur excessive costs. Thus, a robust process for abottom-up or additive manufacturing of permanent magnets, for example,starting from nanoparticle feedstocks is highly desirable.

In contemplated approaches, hard magnetic nanoparticles may formnanocomposite magnets with a high energy product and reduced RE elementcontent. According to various embodiments described herein, thesynthesis and controlled assembly of SmCo₅-based nanoparticles mayenable flexibility in the dimensions and design of the prototype orfinal part. Moreover, high coercivity of SmCo₅-based may be achieved bycontrolling the nanometer to micron sized grains in the magnetmicrostructure since coercivity increases with decreasing grain size.However, controlled synthesis of large scale ferromagnetic single domainparticles has been an obstacle to manufacturing permanent magnets.

Contemplated approaches to synthesize SmCo nanoparticles havedemonstrated problematic drawbacks for use in the manufacture ofpermanent magnets. Synthesis of reduced SmCo₅ nanoparticles from metalsalts (e.g. by chemical reducing agents or high temperatures) by directsolution phase synthesis has been challenging due to the extremelynegative reduction potential of Sm(1) and the susceptibility of Sm(0)nanoparticles to re-oxidation under synthesis conditions. Alternativeapproaches to synthesize SmCo nanoparticles have includedsurfactant-assisted ball milling to deconstruct bulk SmCo tonanoparticles; however, this method lacks the ability to control theresulting particle size or shape of the nanoparticles.

Methods to synthesize SmCo nanoparticles based on traditional thermaldecomposition in organic solvents have shown some promise. For instance,sintered SmCo₅ can been synthesized from nanoparticles of core-shellCo@Sm₂O₃ nanoparticles followed by reduction under calcium (Ca) metalwith 8 kOe coercivity at 300 K. More recently, coercive SmCo₅nanoparticles, with CaO coatings to prevent sintering, have beensynthesized from an oxide using molten Ca as a reductant and KCl as amolten solvent to assist interfacial diffusion. The resulting discreteSmCo₅ nanoparticles had a coercivity of 7 kOe at 300 K. However,nanoparticle synthesis based on traditional thermal decomposition inorganic solvents can be difficult to scale, and the surfactants used inthe process involve additional steps to remove the surfactants prior toreduction. Moreover, aggregation of magnetic particles in solution andin free space pose challenges using additive manufacturing to form bulkmagnets from ferromagnetic nanoparticles. Thus, methods for scaling-upand fabricating bulk nanostructured magnets remain elusive.

Various embodiments described herein include a simple, flexible methodfor manufacturing high coercivity samarium cobalt (SmCo₅) and neodymiumiron boride (Nd—Fe—B) magnets that may be compatible with additivemanufacturing. Moreover, methods described herein do not include addinga polymer binder. Some embodiments describe SmCo₅ oxide and Nd—Fe—Bparticles, as the feedstock for a magnet, deposited into near-net shapeparts using additive manufacturing techniques such as electrophoreticdeposition (EPD). Various embodiments describe a process of convertingoxide nanoparticles, deposited into near net-shape parts, directly topermanent magnets using calcium vapor during annealing.

According to various approaches described herein, oxide particles may beshaped into a nonmagnetic part prior to the process that converts thematerial into a magnet. It would be advantageous to deposit the oxideparticles when the particles are neither air sensitive nor magnetic.Furthermore, the depositing process of the oxide particles may be doneat ambient temperature on the bench top in the laboratory.

Embodiments described herein include synthesis of SmCo-based permanentmagnets from SmCo₅ oxide nanoparticles with room temperaturecoercivities two to three times larger than coercivities of the bestperforming commercial magnets. According to some embodiments, theprocess may begin with large-scale, surfactant-free, tunable synthesisof mixed SmCo oxide nanoparticles using flame spray pyrolysis therebysynthesizing mixed oxide particles in bulk (e.g. tens of grams tokilograms per batch). Moreover, various embodiments demonstrate facileassembly of SmCo nanoparticles from solution phase suspensions usingadditive manufacturing techniques.

According to various embodiments described herein, a magnet includes athree-dimensional (3D) structure with nanoscale features, where thethree-dimensional structure has a near net shape corresponding to apredefined shape. For the purposes of this application, a near net shapeis defined that the initial design shape of a structure is close to thefinal net shape of the structure, less about a 5% change in shape of theinitial design. In some approaches, a near net-shape may be defined as afinal shape having less than a 1% change in shape of the initial designin smooth structures, such as, for example, but not meant to belimiting, cylinders, cubes, arcs, etc.

A 3D structure may have nanoscale features such as pores, laths, or barswhere an average diameter of the features is less than 1000 nm,preferably less than 500 nm, more preferably less than 250 nm. Thesefeatures may enable backfilling of the microstructure with a secondmaterial to improve mechanical properties, such as strength, fracturetoughness, etc. Moreover, backfilling 3D structures having nanoscalefeatures with a second material may also improve corrosion resistance,improve the magnetic properties, etc.

In some approaches, features of the 3D structure may represent sinteredremnants of the particles that form the 3D structure. In someapproaches, nanoscale features of the 3D structure may representsintered remnants having an average diameter of about a nanoscale range.

In some approaches the magnet may be a permanent magnet. In preferredapproaches, the magnet includes a rare earth element that may be a lightrare earth element, for example, but not limited to, samarium (Sm),neodymium (Nd), etc. In some approaches, the magnet includes samariumcobalt. In some approaches, the magnet includes neodymium iron boride(Nd—Fe—B). For example, but not meant to be limiting in any way, aNd—Fe—B magnet may be formed with Sm—Co to provide very high coercivityin selected areas (e.g. corners and edges.)

In some approaches, the permanent magnet formed by methods describedherein may have an energy product greater than 5 Mega-Gauss-Oersted(MGOe) to temperatures of at least 200° C.

In some approaches, the magnet may include calcium. In some approaches,the magnet may include elemental calcium. In other approaches, themagnet may include calcium oxide. In yet other approaches, the magnetmay include elemental calcium and calcium oxide.

FIG. 1 depicts a structure 100 of a thin foil magnet, in accordance withone embodiment. As an option, the present structure 100 may beimplemented in conjunction with features from any other embodimentlisted herein, such as those described with reference to the other FIGS.Of course, however, such structure 100 and others presented herein maybe used in various applications and/or in permutations which may or maynot be specifically described in the illustrative embodiments listedherein. Further, the structure 100 presented herein may be used in anydesired environment.

In some approaches, the magnet may be a foil magnet. In some approaches,the foil magnet may be a thin foil magnet. In some approaches, thethickness of the thin foil magnet is in a range of greater than about500 nanometers and less than about five millimeters. A thickness of amagnet is measured in the z-direction, where the z-direction isperpendicular to an x-y plane. In some approaches, the layers of a thinfoil magnet may be deposited on an x-y plane and having a plurality oflayers in a z-direction.

As shown in the schematic drawing of a structure 100 in FIG. 1 depictingan example of a thin foil magnet, the dimensions of the thin foil magnetmay be arbitrary. For example, the structure 100 may be square at oneend 102 with more complicated angles, sides, etc. at the other end 104.Sizes of the thin foil magnet may be in a range for application inmicro-robotics, (e.g. less than 1 mm). As shown as an example only andis not meant to be limiting in any way, for structure 100, the height hmay be 50 μm, length l may be 1 mm, and width w may be 0.25 mm.

In preferred approaches, a thin foil magnet is formed with a controlledshape and having full density which would be above 90% of thetheoretical density (7.7-8.6 g/cm³ for SmCo₅ and 7-7.8 g/cm³ for Nd—Fe—Bbased magnets).

Using calcium vapor reduction methods as described herein, the resultingSmCo₅ permanent magnet structure may demonstrate coercivity at roomtemperature (i.e. the room temperature is between 20° C. and 28° C.)much higher than typical for bulk SmCo₅. In some approaches, the magnetcoercivity of a SmCo₅ permanent magnet at room temperature may be atleast 60 kOe. In some approaches, the room temperature coercivity of abulk cast SmCo₅ permanent magnet, as a measurement of demagnetizingfield strength, may be nearly 68 kOe. In other approaches, the magnetcoercivity of a drop-cast SmCo₅ permanent magnet at room temperature mayup to 80 kOe.

In sharp contrast to conventional permanent magnets which demonstrate adecline in coercivity linearly with increased temperature, variousembodiments described herein demonstrate highly coercive magnets attemperatures higher than current industry limits (around 300° C.). Forexample, in various embodiments, the magnetic coercivity of SmCo₅permanent magnets may be greater than 10 kOe at temperatures of about500° C.

According to some embodiments, the permanent magnet may have a highsquareness factor. In some approaches, the permanent magnet may performwith a high magnetization and high coercivity at temperatures at leastabout 500° C., where the coercivity may still exceed 10 kOe. Further,the remnant magnetization may not be significantly reduced at theseelevated temperatures making such a magnet useful for motor/generatorapplications at extreme temperatures. Moreover, a permanent magnetformed from small, refined nanoparticles as described herein provides anopportunity to overcome Brown's paradox that the observed value ofmagnetism of bulk magnetic material cannot exceed about ⅓ of thetheoretical maximum. In other words, the experimental value of magnetismof permanent magnets formed by methods described herein may come closerto the theoretical value of magnetism for the magnet than has previouslybeen achievable.

FIG. 2 depicts a flowchart for a method 200 for forming a permanentmagnet, in accordance with one embodiment. As an option, the presentmethod 200 may be implemented to structures such as those shown in theother FIGS. described herein. Of course, however, this method 200 andothers presented herein may be used to form structures for a widevariety of devices and/or purposes which may or may not be related tothe illustrative embodiments listed herein. Further, the methodspresented herein may be carried out in any desired environment.Moreover, more or less operations than those shown in FIG. 2 may beincluded in method 200, according to various embodiments. It should alsobe noted that any of the aforementioned features may be used in any ofthe embodiments described in accordance with the various methods.

Method 200 begins with step 202 of forming a three dimensional (3D)structure that includes oxidized precursor metal particles. In variousembodiments, the precursor metal particles may be precursor metalnanoparticles.

In some approaches of method 200, the precursor metal particles may beoxidized before forming a three dimensional structure. The first step202 may include a prior step of preparing oxidized precursor metalparticles (e.g. SmCo₅ oxide, Nd—Fe—B oxide, etc.) for forming a 3Dstructure on a substrate.

In various embodiments described herein precursor metal particles may bedefined as precursor metal material that may not be sensitive to air.The precursor metal particles may not be magnetic before forming a 3Dstructure. The precursor metal particles may not be magnetic beforereducing and annealing the formed 3D structure. In exemplary approaches,precursor metal particles have negligible magnetic properties. Moreover,in the processes described herein, the precursor metal particles may beeasily dispersed in solution as compared to the difficulty of dispersingmagnetic particles in solution.

In some approaches, step 202 may include forming a 3D structure by drypressing a powder of the oxidized precursor metal particles.

In other approaches, before forming the three dimensional structure, themethod may include suspending oxidized precursor metal particles in asolution. Moreover, step 202 may include forming a 3D structure bydepositing oxidized precursor metal particles on a substrate from asolution of suspended the oxidized precursor metal nanoparticles in thesolution. In some approaches, the precursor magnet particles may besmall enough to create a particle suspension in a solution of solvent.

In some approaches, the liquid component of the solution may be anonpolar solvent, a polar solvent, etc. In some approaches, the liquidcomponent of the solution may be a combination of nonpolar solvent and apolar solvent. For example, but not meant to be limiting, the liquidcomponent of the solution may be ethanol. In various embodiments theliquid component of the solution is an evaporative solution.

In an exemplary embodiment, the method includes preparing about asolution of precursor SmCo₅ oxide particles having an average size in arange of about 20 nm to about 200 nm in diameter. The SmCo₅ oxideparticles may be synthesized in a bulk quantity using a process ofsynthesizing of flame spray pyrolysis.

In some approaches, the method to deposit the particles from thesolution onto a substrate may include dropcasting such that a solutionof particles is dripped onto the substrate and the solution isevaporated from the dropcast form of particles on the substrate.

In some approaches, after forming the three dimensional structure, themethod includes evaporating a liquid component of the solution from theformed three dimensional structure of oxidized precursor metalparticles.

Various approaches include forming a 3D structure of precursor metalparticles that may not be sensitive to air (e.g. oxidization) and maynot have magnetic properties, thereby allowing facile and reproducibleparticle dispersion in suspension, which is optimal for additivemanufacturing techniques, for example, but not limited to,electrophoretic deposition (EPD) and direct ink writing (DIW).

In some approaches, the method to deposit the particles from a solutionof suspended particles onto a substrate may involve EPD which includesusing electric fields to direct and deposit oxidized precursor metalparticles above an electrode. Various approaches using EPD allowsflexible material synthesis and defined nanoparticle packing densitydepositing particles on a substrate using electric fields. In someapproaches using EPD, the substrate is electrically conductive. In someapproaches of EPD, the substrate may be an electrode. In someapproaches, the shape of the electrode, substrate, etc. may define theshape of the final magnet part. In various approaches, substratematerials that may be used in a furnace include stainless steel,graphite, molybdenum, etc.

Moreover, in some approaches, an EPD device may include nonplanarelectrodes or custom electrodes to form custom shapes during EPD. Thus,permanent magnets with custom shapes may be produced rapidly andinexpensively.

In other approaches, a 3D structure may be formed using DIW, anextrusion technique of additive manufacturing that relies onshear-thinning ink formulations. In some approaches, forming the 3Dstructure includes extruding an ink including the oxidized precursormetal nanoparticles onto the substrate.

Both EPD and DIW approaches to form a 3D structure on a substrate mayfacilitate a rapid production of small magnets with thicknesses ofseveral millimeters.

In some approaches, forming the 3D structure includes forming a mold ofthe oxidized precursor metal nanoparticles in a solution.

As an option, in approaches where precursor metal nanoparticles weresuspended in solution for forming the 3D structure on the substrate,step 204 of method 200 includes evaporating the liquid component of thesolution from the formed 3D structure of oxidized precursor metalnanoparticles. In some approaches, the 3D structure may be formed on asubstrate. In various approaches, the conditions for a slow evaporationof the liquid component of the solution of precursor metal nanoparticlesmay depend on the liquid component and type of structure, e.g. a thinfoil or a 3D structure. For instance, in some approaches in which theprecursor nanoparticles are suspended in ethanol, evaporation of theliquid component from a molded structure may involve drying thestructure at an elevated temperature (e.g. about 90° C.) for aneffective amount of time to evaporate the liquid component of thesolution (e.g. about 3 to 5 days). In other approaches of oxidizedprecursor metal nanoparticles suspended in ethanol, evaporation ofliquid component of the solution from a formed structure may involvelyophilization and solvent exchange. In yet other approaches,evaporation of liquid component of the solution from the formedstructures of precursor nanoparticles may involve supercriticalextraction.

Step 206 of method 200 includes heating the formed 3D structure in anatmosphere including a calcium vapor and a gas for reducing the oxidizedprecursor metal particles of the 3D structure. In some approaches, thegas may be a forming gas. In some approaches, step 206 includesconverting deposited material from step 202 to a reduced pre-magneticform by heating the deposited material in the presence of calcium vaporand forming gas (for example but not meant to be limiting, 4% hydrogenin argon). In approaches where the 3D structure is formed from asolution of suspended oxidized precursor metal particles, step 206includes converting dry deposited material from step 204, in which anyresidual solution, e.g. the liquid component of the solution, in theformed 3D structure has been evaporated, to a reduced pre-magnetic form.

In various approaches, the formed 3D structure may be reduced andannealed by heating (e.g. sintering) in the presence of calcium vaporthereby allowing the sample geometry of the 3D structure to bemaintained. In one approach, step 206 of heating the formed 3D structurefor reducing and annealing the oxidized precursor metal particlesincludes heating at a temperature in a range of about 800° C. to about1000° C. in an atmosphere comprising a calcium vapor and a forming gas.

In various approaches of step 206, there is no direct contact betweenthe oxide particles of the 3D structure and the calcium granules.Furthermore, as understood by one skilled in the art, contacting anoxide particle powder with calcium can have deleterious effects. Studieshave shown that heating a mixture of SmCo₅ oxide/potassium chloride withsolid calcium granules results in a thick layer of melted calciumgranules on the substrate of the SmCo₅-sintered magnet. Consequently,removing the layer of melted calcium granules from the combinedSmCo₅-melted calcium magnet product causes the underlying SmCo₅ materialto break, thereby resulting in increased difficulty to form magnets of apre-defined size.

Step 206 includes forming the calcium vapor from a bed of calciumgranules positioned a distance d from the formed three dimensionalstructure. The distance d may be greater than zero millimeters (mm). Insome approaches, the distance d may be about 2 millimeters. Variousembodiments described herein use vapor technique with calcium vaporreduction which allows a clean reduction of the oxide without contact ofthe calcium granules with the SmCo₅ oxide material such that the finalpart may be ready to use directly after reduction. In addition, thesample geometry of the initial design of the magnet may be maintained inthe final product.

In various approaches, the sintering of step 206 may result in sinteredremnants of the reduced particles metal particles. In some approaches,sintered remnants may represent features of the 3D structure. Thefeatures of the sintered 3D structure may have an average diameter ofnanoscale range. For example, the features of the sintered 3D structuremay be less than 1000 nm, preferably less than 500 nm, more preferablyless than 250 nm.

FIGS. 3A-3C depicts a series of schematic diagrams for a process 300 forreducing oxidized precursor metal nanoparticles in a formed 3Dstructure, in accordance with one embodiment. As an option, the presentprocess 300 may be implemented to structures such as those shown in theother FIGS. described herein. Of course, however, this process 300 andothers presented herein may be used to form structures for a widevariety of devices and/or purposes which may or may not be related tothe illustrative embodiments listed herein. Further, the methodspresented herein may be carried out in any desired environment.Moreover, more or less operations than those shown in FIGS. 3A-3C may beincluded in process 300, according to various embodiments. It shouldalso be noted that any of the aforementioned features may be used in anyof the embodiments described in accordance with the various methods.

FIG. 3A illustrates a cross section of the process 300 of calcium vaporreduction, according to one embodiment. As illustrated in FIG. 3A, asample 302 having a 3D structure of metal oxide powder/nanoparticlesdeposited on a substrate 304 may be placed above a bed 308 ofcalcium-based granules 306. It is important to note that the drawing inFIG. 3A represents the components of the process 300 and may not bedrawn to scale. In some approaches, the substrate 304 may be a materialto support the sample 302 of metal oxide powder/nanoparticles; forexample, but not meant to be limiting in any way, the substrate may begraphite, steel mesh, molybdenum, etc.

In some approaches, calcium-based granules 306 may be placed in a bed308, for example, stainless steel boat, and the sample 302 of metaloxide powder/nanoparticles may be positioned with an air gap between thecalcium-based granules 306 and the sample 302 of metal oxidepowder/nanoparticles on a substrate 304. In some approaches, thedistance d between the calcium-based granules 306 and the substrate 304may be in a range of about greater than 2 mm to less than about 50 mm.In some approaches, the distance d may be in a range of about greaterthan 2 mm to less than about 10 mm.

FIG. 3B is a photographic image of a container 312 that may be used inthe process 300 of calcium vapor reduction as described in method 200(FIG. 2). In some approaches, the container 312 includes a hollowed bed308 for the calcium-based granules 306. In preferred approaches, thesample 302 of metal oxide powder/nanoparticles on a substrate 304 may bepositioned at a distance d from the calcium-based granules 306, suchthat the sample 302 of metal oxide powder/nanoparticles may not makecontact with the calcium-based granules 306. In some approaches, thedistance d is greater than 0 mm.

In some approaches of step 206 of method 200 (FIG. 2), the lid 313 ofthe container 312 may be lightly closed over the bed 308 of thecontainer before being placed in the furnace.

In some embodiments, the sample 302 of metal oxide powder/nanoparticlesmay be reduced and annealed to a metal at elevated temperatures, forexample, a temperature in a range of about 800° C. to about 1000° C., inan atmosphere that includes a calcium vapor 310 from the heated calciumgranules 306. In preferred approaches, the heating of step 206 of method200 may occur at least at the temperature of about the meltingtemperature of calcium. FIG. 3C. illustrates a cross section of thepartially closed container 312 as illustrated in FIG. 3B that includesthe sample 302 of the metal oxide powder/nanoparticles positioned abovea bed 308 of calcium-based granules 306.

As shown in FIG. 3C, the partially closed container 312 may be exposedto the forming gas 316 in a controlled environment 314 (e.g. container,space, etc.). In some approaches, as the forming gas 316 flows acrossthe partially closed container 312, the sample 302 of the metal oxidepowder/nanoparticles is exposed to calcium vapor 310 (as illustrated inFIG. 3A) formed from the heated calcium-based granules 306 in thepresence of the forming gas 316. In preferred approaches, the flow rateof the forming gas 316 may be determined in a range between being highenough to maintain an atmosphere of the forming gas 316 above the samplebut low enough to allow the calcium vapor 310 (FIG. 3A) to contact thesample 302 (e.g. the forming gas should not displace the calcium vaporat the sample).

In some approaches, the forming gas 316 may include an inert gas. Insome approaches, the forming gas may be a mixture of hydrogen and aninert gas, usually Ar, He, or N₂. In some approaches, N₂ may function asan inert gas.

In one approach, the forming gas 316 may be a mixture of argon gas withhydrogen gas. In another approach the forming gas 316 may be a mixtureof helium gas with hydrogen gas.

In some approaches, the gas in the atmosphere for reducing the oxidizedprecursor metal nanoparticles may be argon gas. In other approaches, thegas in the atmosphere for reducing the oxidized precursor metalnanoparticles may be helium gas.

Looking back to FIG. 2, step 208 of the method 200 to form a magnetincludes applying a magnetic field to the metal 3D structure foraligning spins of the metal, where the metal 3D structure is transformedto the magnet. In some approaches, step 208 may include a thermalannealing step in which an external magnetic field is applied during theheating process of the metal 3D structure. As illustrated in FIG. 3Cdepicting a cross section of a heating process, step 208 may includeapplying a magnetic field 318 during the conversion process to align thespins in the magnetic particles of the sample in the reducing container312. In some approaches, the final magnet form may have a netmagnetization in the direction of the applied magnetic field 318.

A magnetic field 318 may be applied (N←S) during the annealing processof the sample 302 of metal oxide powder/nanoparticles. In otherapproaches of step 208 of method 200, the magnetic field 318 may beapplied after the heating step 206 of method 200 when the sample 302 ofmetal oxide powder/nanoparticles has been transformed to a metal.

Various embodiments described herein include a calcium vapor reductiontechnique that creates near net shape magnets. According to oneembodiment, EPD with solutions of nanoparticle magnet precursors may berecycled during the EPD process thereby resulting in near-zero (e.g.less than 0.1%) loss of starting materials.

According to various embodiments, custom shapes of permanent magnets maybe created from electrode profiles that may be produced rapidly andinexpensively. EPD can rapidly produce parts with thicknesses of severalmillimeters. Furthermore, the calcium vapor reduction technique showspromise for producing magnets with room temperature coercivities (whichin part determines the energy product) twice as large as magnetsproduced using traditional methods. Because coercivity declinesmonotonically with temperature, these additively manufactured magnetsmay find application at temperatures higher than current industry limits(around 300° C.).

FIGS. 4A-4B depict a method 400 for forming a thin foil permanentmagnet, in accordance with one embodiment. As an option, the presentmethod 400 may be implemented to structures such as those shown in theother FIGS. described herein. Of course, however, this method 400 andothers presented herein may be used to form structures for a widevariety of devices and/or purposes which may or may not be related tothe illustrative embodiments listed herein. Further, the methodspresented herein may be carried out in any desired environment.Moreover, more or less operations than those shown in FIGS. 4A-4B may beincluded in method 400, according to various embodiments. It should alsobe noted that any of the aforementioned features may be used in any ofthe embodiments described in accordance with the various methods.

As illustrated in the flow chart in FIG. 4A, method 400 begins with step402 of forming a thin foil having a plurality of layers of oxidizedprecursor metal nanoparticles. As illustrated in FIG. 4B, step 402 maybe expanded to include several sub-steps 402 a, 402 b, 402 c, 402 d forforming a thin foil having a plurality of layers. The sub-steps 402 a,402 b, 402 c, 402 d may be repeated until a thin foil having a pluralityof layers reaches a desired thickness for formation of the thin foil. Invarious approaches, the precursor metal nanoparticles may be oxidizedbefore forming the first, n layers of precursor metal nanoparticles ofthe thin foil. In one approach, the oxidized precursor metalnanoparticles may be samarium cobalt oxide. In another approach, theoxidized precursor metal nanoparticles may be neodymium iron borideoxide. In some approaches, the oxidized precursor metal nanoparticles ofthe first layer may be different from the precursor metal nanoparticlesof the second layer. In other approaches, the layers may be formed fromthe same solution of suspended oxidized precursor metal nanoparticles.

A first sub-step 402 a of forming a thin foil having a plurality oflayers of oxidized precursor metal nanoparticles includes forming afirst layer of oxidized precursor metal nanoparticles on a substrate. Insome approaches, the oxidized precursor metal nanoparticles aresuspended in a solution. Exemplary examples of an evaporative liquidcomponent of a solution include a nonpolar solvent, polar solvent, or acombination thereof.

In some approaches, step 402 a may include methods for forming a layermay include methods such as drop-casting, dripping, etc. a solution ofsuspended precursor metal nanoparticles onto a substrate. In a preferredapproach, forming the n layers of oxidized precursor metal nanoparticleson the substrate includes dropcasting a solution of suspended oxidizedprecursor metal nanoparticles on the substrate.

In other approaches, step 402 a may include forming a layer byelectrophoretic deposition of the nanoparticles in an EPD system. Invarious approaches, electrophoretic deposition using EPD devices notspecifically described herein may be chosen, selected, and optimizedaccording to any number of factors, such as size limitations, powerrequirements, formation time, etc., as would be known by one of skill inthe art upon reading the present disclosure.

Step 402 b includes evaporating the liquid component of the solutionfrom the first layer of oxidized precursor metal nanoparticles. Invarious approaches, the conditions for a slow evaporation of the liquidcomponent of the solution of the oxidized precursor metal nanoparticlesmay depend on the liquid component and the desired thickness of eachdeposited layer of oxidized precursor metal nanoparticles of the thinfoil. For instance, in some approaches of oxidized precursor metalnanoparticles suspended in ethanol, evaporation of liquid component ofthe solution from a layer of a thin foil structure may involvelyophilization and solvent exchange. In yet other approaches,evaporation of liquid component of the solution from the formedstructures of oxidized precursor nanoparticles may involve supercriticalextraction.

After the evaporating, step 402 c includes forming at least one secondlayer of oxidized precursor metal nanoparticles above the first layer ofoxidized precursor metal nanoparticles.

In preferred approaches, step 402 c may include drop-cast subsequentlayers of oxidized precursor metal nanoparticles in thicker layerscompared to conventional layers of thin foil magnets (e.g. in a range ofabout 1 micron to about 100 microns). Without wishing to be bound by anytheory, it is believed that thicker drop-cast layers may generateincreased magnetic properties (e.g. a final thin foil magnet having ahigh coercivities of at least 60 kOe).

Step 402 d includes evaporating the liquid component of the solutionfrom the at least one second layer of oxidized precursor metalnanoparticles.

In further approaches, steps 402 c and step 402 d to forming n layers ofprecursor metal nanoparticles on a n−1 layer of evaporated precursormetal nanoparticles for forming a thin foil having a plurality of layersof oxidized precursor metal nanoparticles. In preferred approaches, theformed thin foil may have a pre-defined thickness.

After forming a thin foil having a plurality of layers of precursormetal nanoparticles where the thin foil has achieved a pre-definedthickness, method 400 continues (as illustrated in FIG. 4A) with step404 of reducing the oxidized precursor metal nanoparticles of the thinfoil in an atmosphere comprising a calcium vapor and a gas. In someapproaches, the gas may be a forming gas. A thin foil having layers ofreduced metal nanoparticle layers may result in a thin foil havinglayers of metal.

In various approaches, step 404 of reducing the oxidized precursor metalnanoparticles of the formed thin foil includes heating the oxidizedprecursor metal nanoparticles to a temperature in a range of about 800°C. to about 1000° C. in an atmosphere including a calcium vapor and aforming gas as described herein. In some approaches, the forming gas maybe an inert gas mixed with hydrogen gas.

In various approaches, the calcium vapor may be formed from a bed ofcalcium granules positioned a distance d from the formed thin foil of aplurality of layers of oxidized precursor metal nanoparticles. In someapproaches, the distance d is greater than zero millimeters. Inpreferred approaches, there is no contact between the calcium granulesand the plurality of layers of the formed thin foil.

Step 406 includes applying a magnetic field to the reduced precursormetal nanoparticles of the thin foil. The applied magnetic field alignsthe plurality of spins of the metal nanoparticles, where the thin foilhaving layers of metal is transformed to a thin foil magnet.

In some approaches, step 406 may include a thermal annealing step inwhich an external magnetic field is applied during the heating processof the metal 3D structure. As illustrated in FIG. 3C depicting a crosssection of a heating process, step 406 may include applying a magneticfield during the conversion process to align the spins in the magneticparticles such that the final magnet form will have a net magnetizationin one direction, according to some approaches.

A magnetic field 318 may be applied (N←S) during the annealing processof the sample 302 of metal oxide powder/nanoparticles. In otherapproaches of step 406, the magnetic field 318 may be applied after theheating step 406 when the sample 302 of metal oxide powder/nanoparticleshas been transformed to a metal.

Experiments

Materials

Sm_(x)Co_(y)O_(z) (nominally SmCo₅O₉) nanoparticles were custom producedby Nanocerox (Ann Arbor, Mich.). The particles were synthesized usingFlame Spray Pyrolysis (FSP) using controlled ratios of Sm and Co saltsdissolved in organic solvents. Absolute ethanol was used as received;tetraglyme was purchased from Sigma-Aldrich (St. Louis, Mo.) and used asreceived. One millimeter thick graphite electrodes were purchased fromOhio Carbon Blank (Willoughby, Ohio). Calcium granules, redistilled, 16mesh, 99.5% were purchased from Alfa Aesar (Haverhill, Mass.).

Methods

Nanoparticle Deposition: Dropcasting to Form a Thin Magnetic Foil

Suspensions of nanoparticles were prepared by mixing the particles andabsolute ethanol to a concentration between 1 and 2 volume % solids orapproximately 50 mg/ml particles in ethanol.

A thin magnetic foil was prepared by drop-casting, or repeatedlydripping the solution onto the substrate and allowing the solvent toevaporate until the desired foil thickness is reached. A typical samplesurface density (e.g. mass per area) for drop-cast samples was >0.02g/cm².

Nanoparticle Deposition: Electrophoretic Deposition

Deposition of nanoparticles for thicker free-standing magnets and fornear-net shape manufacturing of magnets included the followingtechniques.

EPD was used to deposit nanoparticles from an ethanol solution (at aconcentration of approximately 1 vol %) onto the graphite electrodes.The setup consisted of two graphite electrodes inserted into a stirringbath of the nanoparticles. A power supply was used to apply a voltageacross the electrodes. A typical electric field was 40 V/cm. After 5minutes of deposition, 2-4 mm thick foils were produced on the cathode.To direct the shape of the deposited magnet, the graphite was masked toblock the field using electrical tape. To avoid cracking of magneticfoil, different techniques were used to slow the drying process,including lyophilization and solvent exchange.

Nanoparticle Deposition: Molding and Extrusion Additive Manufacturing

For molding and extrusion techniques, a 14 vol % suspension of SmCo₅O₉nanoparticles was mixed with Tetraglyme using a Flacktek centrifugalmixer (Landrum, S.C.) at 3500 rpm for 5 minutes. The resultingshear-thinning paste was applied to silicone rubber molds using aspatula or extruded using a DIW printing system. Using DIW, theink-loaded syringes were loaded onto a three-axis micropositioning stage(Aerotech, Inc, Pittsburgh, Pa.). A constant displacement drive was usedto deliver the ink through nozzle diameters of 250 μm such that thelinear feed rate was 3 mm s⁻¹. After molding or extrusion of the paste,the part was dried slowly to avoid cracking by covering with a glasspetri dish and placed at 90° C. for 3 to 5 days until drying wascomplete.

Calcium Vapor Reduction of Powder

A one-step process was performed that included sintering and reducingthe deposited SmCo oxide materials while retaining their shape. First,calcium granules were placed in the bed of a stainless steel boat. Astainless steel screen was placed above the calcium granules to providean air gap between the sample sitting on the screen and the moltencalcium. The SmCo oxide material, either on a graphite electrode orremoved from the substrate was then placed directly on the screen. Theboat was then covered loosely with a lid, and loaded into the tubefurnace. Forming gas (4% H₂ in Ar) was flowed over the sample, and thefurnace was heated to a temperature above the melting temperature ofcalcium (842° C.), typically 875° C. Heating time was varied between 30minutes and 24 hours. After the desired annealing time, the furnace wasshut off and rapidly cooled in order to retain the desired SmCo₅ phase.A typical initial cooling rate over the first ten minutes was 40° C. perminute.

Post Processing

For some applications and for characterization it was desirable toremove the calcium oxide from the sintered magnet. The calcium wasremoved from the monolithic sintered magnets by soaking them overnightin water saturated with bubbling argon gas.

Magnetometer Measurements

The samples were loaded into gelatin capsules partially filled withpolyethylene glycol powder, 3350 molecular weight, which was initiallyheated above its melting point in order to lock the sample in placeunder applied field.

FIG. 5A is a plot depicting the maximum energy stored (BH)_(max) (▪) andthe coercivity H_(c) (●) of the magnets measured at temperatures rangingfrom 300 to 1000 kelvins (K) (or 20 to 800° C.), according to variousembodiments described herein. As shown, at temperatures up to about 500°C., the magnets had a coercivity above 20 kOe and a (BH)max of greaterthan 3 MGOe.

FIG. 5B is a plot depicting magnetization (kG) compared to the appliedmagnetic field (kOe) of a representative magnet formed according toembodiments described herein and measured at a series of increasingtemperatures. As shown, the remnant magnetization was constant to atleast 230° C., and decreased gradually at higher temperatures. Thecoercivity exceeded 60 kOe at 30° C. and was still greater than 10 kOeat 630° C. In particular, at higher temperatures, 230° C., 430° C., and630° C., the magnetization curves were similar to the magnet at 30° C.but with decreasing coercivities.

In Use

Various embodiments described herein use electrophoretic deposition toreduce the amount of metal oxide powders used in metal assembly. Someembodiments describe the manufacture of near net shape permanentmagnets. Various embodiments described herein produce small magnets, ofmillimeter size, thereby providing an advantage in the rapidly expandingmarket of high performance speakers, compact motors, and magneticallydriven actuators.

Some embodiments described herein may produce magnets with roomtemperature coercivities that are twice as large as magnets producedusing traditional methods.

Some embodiments described herein may produce thin strong magnets thatmay be useful in small motor applications, micro-robotics, etc.

The inventive concepts disclosed herein have been presented by way ofexample to illustrate the myriad features thereof in a plurality ofillustrative scenarios, embodiments, and/or implementations. It shouldbe appreciated that the concepts generally disclosed are to beconsidered as modular, and may be implemented in any combination,permutation, or synthesis thereof. In addition, any modification,alteration, or equivalent of the presently disclosed features,functions, and concepts that would be appreciated by a person havingordinary skill in the art upon reading the instant descriptions shouldalso be considered within the scope of this disclosure.

While various embodiments have been described above, it should beunderstood that they have been presented by way of example only, and notlimitation. Thus, the breadth and scope of an embodiment of the presentinvention should not be limited by any of the above-described exemplaryembodiments, but should be defined only in accordance with the followingclaims and their equivalents.

What is claimed is:
 1. A magnet, comprising: a three-dimensionalstructure with nanoscale features, wherein the three-dimensionalstructure has a near net shape corresponding to a predefined shape. 2.The magnet as recited in claim 1, wherein the magnet comprises samariumcobalt, wherein a magnetic coercivity of the magnet at room temperatureis at least 60 kiloOersteds.
 3. The magnet of claim 1, wherein themagnet comprises neodymium iron boride.
 4. The magnet of claim 1,wherein the magnet is a permanent magnet with an energy product greaterthan 5 Mega-Gauss-Oersted to temperatures of at least 200° C.
 5. Themagnet of claim 1, wherein the magnet is a thin foil magnet having athickness in a range of greater than about 500 nanometers and less thanabout five millimeters.
 6. The magnet of claim 1, wherein the magnetcomprises calcium.
 7. A method of making a permanent magnet, the methodcomprising: forming a three dimensional structure comprising oxidizedprecursor metal particles; heating the formed three dimensionalstructure in an atmosphere comprising a calcium vapor and a gas forreducing the oxidized precursor metal particles of the three dimensionalstructure; and applying a magnetic field to the reduced precursor metalparticles of the three dimensional structure.
 8. The method as recitedin claim 7, wherein the oxidized precursor metal particles includesamarium cobalt oxide.
 9. The method as recited in claim 7, wherein theoxidized precursor metal particles include neodymium iron boride oxide.10. The method as recited in claim 7, wherein forming the threedimensional structure comprises dry pressing a powder of the oxidizedprecursor metal particles.
 11. The method as recited in claim 7,comprising: before forming the three dimensional structure, suspendingoxidized precursor metal particles in a solution; and after forming thethree dimensional structure, evaporating a liquid component of thesolution from the formed three dimensional structure of oxidizedprecursor metal particles.
 12. The method as recited in claim 11,wherein forming the three dimensional structure compriseselectrophoretic deposition of the oxidized precursor metal particlesabove an electrode.
 13. The method as recited in claim 11, whereinforming the three dimensional structure comprises forming a mold of theoxidized precursor metal particles in the solution.
 14. The method asrecited in claim 11, wherein forming the three dimensional structurecomprises extruding an ink comprising the oxidized precursor metalparticles onto a substrate.
 15. The method as recited in claim 11,wherein the liquid component of the solution is selected from the groupconsisting of: nonpolar solvent, polar solvent, and a combinationthereof.
 16. The method as recited in claim 7, wherein heating theoxidized precursor metal particles of the formed three dimensionalstructure comprises heating the formed three dimensional structure to atemperature in a range of about 800 degrees Celsius to about 1000degrees Celsius in an atmosphere comprising the calcium vapor and thegas.
 17. The method as recited in claim 16, comprising forming thecalcium vapor from a bed of calcium granules positioned a distance fromthe formed three dimensional structure, wherein the distance is greaterthan zero millimeters.
 18. The method as recited in claim 16, whereinthe gas is a forming gas.
 19. The method as recited in claim 18, whereinthe forming gas comprises an inert gas mixed with hydrogen gas.
 20. Themethod as recited in claim 19, wherein the inert gas is selected fromthe group consisting of: argon and helium.
 21. A method of making a thinfoil magnet, the method comprising: forming a thin foil having aplurality of layers of oxidized precursor metal nanoparticles, theforming of the thin foil comprises: forming a first layer of oxidizedprecursor metal nanoparticles on a substrate, wherein the oxidizedprecursor metal nanoparticles are suspended in a solution; evaporating aliquid component of the solution from the first layer of oxidizedprecursor metal nanoparticles; after the evaporating, forming at leastone second layer of oxidized precursor metal nanoparticles above thefirst layer of oxidized precursor metal nanoparticles; and evaporatingthe liquid component of the solution from the at least one second layerof oxidized precursor metal nanoparticles, wherein the thin foil has aplurality of layers of oxidized precursor metal nanoparticles, whereinthe thin foil has a pre-defined thickness; reducing the oxidizedprecursor metal nanoparticles of the thin foil in an atmospherecomprising a calcium vapor and a gas; and applying a magnetic field tothe reduced precursor metal nanoparticles of the thin foil.
 22. Themethod as recited in claim 21, wherein the oxidized precursor metalnanoparticles are selected from the group consisting of: samarium cobaltoxide and neodymium iron boride oxide.
 23. The method as recited inclaim 21, wherein forming the thin foil comprises forming at least onelayer by dropcasting the oxidized precursor metal nanoparticles on thesubstrate, wherein the oxidized precursor metal nanoparticles aresuspended in the solution.
 24. The method as recited in claim 21,wherein the liquid component of the solution is selected from the groupconsisting of: nonpolar solvent, polar solvent, and a combinationthereof.
 25. The method as recited in claim 21, wherein reducing theoxidized precursor metal nanoparticles comprises heating the oxidizedprecursor metal nanoparticles to a temperature in a range of about 800degrees Celsius to about 1000 degrees Celsius in an atmospherecomprising the calcium vapor and the gas.
 26. The method as recited inclaim 21, comprising forming the calcium vapor from a bed of calciumgranules positioned a distance from the formed thin foil, wherein thedistance is greater than zero millimeters.
 27. The method as recited inclaim 21, wherein the gas is a forming gas.
 28. The method as recited inclaim 27, wherein the forming gas is an inert gas mixed with hydrogengas.